CN101381362A - Preparation method of thiophen derivate chloromethylation products - Google Patents
Preparation method of thiophen derivate chloromethylation products Download PDFInfo
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- CN101381362A CN101381362A CNA2008101990959A CN200810199095A CN101381362A CN 101381362 A CN101381362 A CN 101381362A CN A2008101990959 A CNA2008101990959 A CN A2008101990959A CN 200810199095 A CN200810199095 A CN 200810199095A CN 101381362 A CN101381362 A CN 101381362A
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Abstract
The invention discloses a method for preparing a chloromethylation product of thiophene derivatives. The thiophene derivatives are prepared into a compound through chloromethylation, and an ionic liquid is taken as catalyst during the chloromethylation reaction process; and the ionic liquid is the catalyst with the advantages of low cost, easy preparation and friendly environment, and the catalyst after reaction can be reused after simple dehydration, so that the method is suitable for industrial mass production. The method has simple technique, short reaction time, high catalytic efficiency, low catalyst amount and high product yield; and high-quality products can be obtained only by extraction delamination and vacuum distillation of reaction products, and the yield can reach between 70 and 92 percent.
Description
Technical field
The invention provides method a kind of cleaning, come the efficient catalytic thiophen derivate chloromethylation products with ionic liquid.Belong to the organic compound preparing technical field.
Background technology
The Blanc chloromethylation is meant that under the Lewis acid catalysis aromatics is handled through formaldehyde, hydrogenchloride, methyl alcohol or chloromethyl ether, Yu Huanzhong introducing-CH
2The process of Cl atomic group.This is reflected at and occupies critical role in the organic synthesis, is widely used in agricultural chemicals, medicine, dyestuff and spices or its intermediate are synthetic.The chloromethyl that imports on the aromatic hydrocarbon ring can change into other group again, as CH
2OH, CHO, CH
2CN, CH
2NH
2, CH
2NRR ', CH
3, CH
2R etc., thus can easily make a series of new derivatives.
The product that is obtained by the chloromethylation substituted thiophene derivant has important use in medicine and polymkeric substance process industry.Existing preparation method adopts protonic acid H mostly
2SO
4, HCl, H
3PO
4Or can generate HCl, H after the hydrolysis
2SO
4ClSO
3Materials such as H are made catalyzer, realize with thiophene derivant, Paraformaldehyde 96 and hydrochloric acid reaction.US2527680 mixes freezing hydrochloric acid soln and cold formalin, with saturated this mixture of hydrogen chloride gas, this mixture is added in the thiophene gradually reacts, and the temperature of reaction mixture is kept below+1 ℃, can obtain productive rate and be 62.7% 2-chloromethyl thiophene.US0161008 under 0 ℃, with thiophene with contain the compound of ketone group, and this mixture is added in the mixture of concentrated hydrochloric acid and formaldehyde, then hydrogen chloride gas is introduced reaction mixture.Reaction finishes the back dilute with water, with solution of potassium carbonate organic phase is washed till neutrality, and the productive rate by gas chromatographic detection product 2-chloromethyl thiophene is 61%.Patent CN200610122703.7 makes catalyzer and solvent with ionic liquid, under 25~100 ℃, with ionic liquid, contain benzene aromatic hydrocarbons, Paraformaldehyde 96, concentrated hydrochloric acid and add successively in the round-bottomed flask that has agitator, thermometer, reflux condensing tube, magnetic agitation, after reaction finishes, resultant thick product is carried out underpressure distillation, and the transformation efficiency of product is between 70%~90%.
Chloromethylation is except carrying out in the organic solvent of classics, and the chloromethylation that carries out aromatic hydrocarbon with phase-transfer catalyst also is proved to be feasible.Wang Minghui etc. are phase-transfer catalyst with the Tetrabutyl amonium bromide, and 2-chlorothiophene and Paraformaldehyde 96, concentrated hydrochloric acid carry out chloromethylation and generate 2-chloro-3-chloromethyl thiophene under 40 ℃, and productive rate is 77.6%.Because ionic liquid can be used as phase-transfer catalyst, so recently existing ionic liquid is used for the report of Blanc chloromethylation, the Deng You congruence is at halogenation 1-alkyl pyridine, 1-methyl-3-alkyl imidazole quaternary ammonium salt etc. and anhydrous AICl
3In the chlorine aluminic acid room-temperature ion liquid body medium that constitutes, attempted the Blanc chloromethylation of benzene and derivative thereof and chloromethyl ether; Merchant's will just waits with [emim] BF
4Chloromethylation as aromatic hydrocarbons such as catalyst toluene has obtained yield preferably.The present invention has used ionic liquid cheap and easy to get to be phase-transfer catalyst, and the chloromethylation of thiophene derivant is carried out in homogeneous phase, has improved the selectivity of conversion of raw material and reaction.
Summary of the invention
The object of the invention provides that a kind of technology is simple, the method for preparing thiophen derivate chloromethylation products of environmental friendliness and high yield.
The present invention realizes by following scheme:
In the there-necked flask that agitator, thermometer, reflux condensing tube are housed, add ionic liquid, thiophene derivant, Paraformaldehyde 96 and hydrochloric acid, after treating that oil bath temperature reaches design temperature, there-necked flask is put into oil bath, the heating while mixing, chloromethylation product and ionic liquid can AUTOMATIC ZONING.Behind the reaction certain hour, carry out oily water separation, product is at oil phase, and catalyst ion liquid is at water, and the ionic liquid of water can be reused after simply dewatering.With gas chromatographic detection productive rate and transformation efficiency.Used ionic liquid is bromo 1-ethyl-3-Methylimidazole, bromo 1-sec.-propyl-3-Methylimidazole, bromo 1-butyl-3-Methylimidazole, bromo 1-amyl group-3-Methylimidazole, bromo 1-is base-3-Methylimidazole, bromo 1-heptyl-3-Methylimidazole, bromo 1-octyl group-3-Methylimidazole, bromo 1-dodecyl-3-Methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole perfluoro octyl sulfonic acid salt, 1-butyl-3-Methylimidazole hexafluorophosphate or chloro 1-butyl-3-Methylimidazole, used ion liquid amount is reaction 1%~16% of thiophene derivant integral molar quantity, temperature of reaction is at 0~70 ℃, normal pressure, the reaction times is 1 hour~12 hours.Add catalyst ion liquid amount preferred value for add 2%~12% of thiophene derivant molar weight, the preferred value of temperature of reaction is at 20~50 ℃, the preferred value in reaction times is 4~10 hours.Raw materials used is substituted thiophene, thionaphthene or substituted benzene thiophthene, and substituent X and Y are any two combinations in hydrogen, halogen, 12 carbon following alkyl, cyano group or the ethanoyl.Halogen is meant chlorine, bromine or iodine.The following alkyl of 12 carbon is meant methyl, ethyl, propyl group, butyl, amyl group, base, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.In order to save production cost, reduce environmental pollution, another characteristics of the present invention are that catalyst ion liquid is recyclable.
Chemical reaction skeleton symbol of the present invention is expressed as follows:
The invention has the beneficial effects as follows:
1. used ionic liquid is a kind of cheap, easy preparation, eco-friendly catalyzer, and reacted catalyzer can reuse after simply dewatering, and is applicable to industrial scale production.
2. technology is simple, and the reaction times is short, the catalytic efficiency height, and catalyst levels is few, the product yield height, and reaction product only needs extracting and demixing, and underpressure distillation can obtain high-quality product, and productive rate can reach 70%~92%.
Embodiment
Further elaborate preparation method of the present invention below by embodiment.
Embodiment one
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-sec.-propyl-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, and magnetic agitation was reacted 6 hours down at 35 ℃; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 93.9%, and 2-chloro-3-chloromethyl thiophene productive rate is 81.7%.
Embodiment two
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-butyl-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 7 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 95.7%, and 2-chloro-3-chloromethyl thiophene productive rate is 85.0%.
Embodiment three
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 97.7%, and 2-chloro-3-chloromethyl thiophene productive rate is 87.5%.
Embodiment four
Take by weighing 3-undecyl thiophene 2.38g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-be base-3-Methylimidazole 0.0010mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-undecyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 45 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 3-undecyl thiophene transformation efficiency is 9.03%, and 3-undecyl-2-chloromethyl thiophene productive rate is 82.5%.
Embodiment five
Take by weighing 2-chloro-3 methyl thiophene 1.325g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-be base-3-Methylimidazole 0.0007mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chloro-3 methyl thiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 30 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chloro-3 methyl thiophene transformation efficiency is 96.3%, and 2-chloro-3-methyl-5-chloro thiotolene productive rate is 85.9%.
Embodiment six
Take by weighing 5-chloro-3-methylbenzene thiophthene 1.827g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-heptyl-3-Methylimidazole 0.0001mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 5-chloro-3-methylbenzene thiophthene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and 5-chloro-3-methylbenzene thiophthene transformation efficiency is 92.6%, and 5-chloro-3-methyl-2-chloromethylbenzene thiophthene productive rate is 78.4%.
Embodiment seven
Take by weighing 7-chloro-3-methylbenzene thiophthene 1.827 (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-amyl group-3-Methylimidazole 0.0006mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 7-chloro-3-methylbenzene thiophthene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 5 hours; Resultant thick product is carried out underpressure distillation, and 7-chloro-3-methylbenzene thiophthene transformation efficiency is 96.02%, and 7-chloro-3-methyl-2-chloromethylbenzene thiophthene productive rate is 76.9%.
Embodiment eight
Take by weighing 2 acetyl thiophene 1.12g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-dodecyl-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2 acetyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 50 ℃, reacted 8 hours; Resultant thick product is carried out underpressure distillation, and the 2 acetyl thiophene transformation efficiency is 96.9%, and 2-ethyl-5-chloromethyl thiophene productive rate is 79.1%.
Embodiment nine
Take by weighing the basic thiophene 1.68g of 2-(0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate 0.0005mol, concentrated hydrochloric acid (36%) 4ml; The basic thiophene of ionic liquid, 2-, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 70 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and the basic thiophene transformation efficiency of 2-is 97.6%, and 2-base-5-chloromethyl thiophene productive rate is 76.5%.
Embodiment ten
Take by weighing 2-decylthiophene 2.24g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid 1-butyl-3-Methylimidazole perfluoro octyl sulfonic acid salt 0.0004mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-decylthiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 3 hours; Resultant thick product is carried out underpressure distillation, and 2-decylthiophene transformation efficiency is 87.8%, and 2-decyl-5-chloromethyl thiophene productive rate is 62.0%.
Embodiment 11
Take by weighing the basic thiophene 2.47g of 2-bromo-3-(0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, the basic thiophene of 2-bromo-3-, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 0 ℃, reacted 10 hours; Resultant thick product is carried out underpressure distillation, and the basic thiophene transformation efficiency of 2-bromo-3-is 94.6%, and 2-bromo-3-base-5-chloromethyl thiophene productive rate is 69.1%.
Embodiment 12
Take by weighing 3-cyano thiophene 1.09g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid chloro 1-butyl-3-Methylimidazole 0.0016mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-cyano thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 3-cyano thiophene transformation efficiency is 85.8%, and 4-cyano group-2-chloromethyl thiophene productive rate is 74.0%.
Embodiment 13
Take by weighing 2-dodecyl thiophene 2.52g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-dodecyl thiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 30 ℃, reacted 1 hour; Resultant thick product is carried out underpressure distillation, and 2-dodecyl thiophene transformation efficiency is 85.2%, and 2-dodecyl-5-chloromethyl thiophene productive rate is 73.0%.
Embodiment 14
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 12 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 99.2%, and 2-chloro-3-chloromethyl thiophene productive rate is 84.9%.
Embodiment 15
Take by weighing 2-acetyl thiophene 1.26g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-ethyl-3-Methylimidazole 0.0002mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-acetyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-acetyl thiophene transformation efficiency is 79.0%, and 2-ethanoyl-5-chloromethyl thiophene productive rate is 62.6%.
Embodiment 16
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0010mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 94.7%, and 2-chloro-3-chloromethyl thiophene productive rate is 78.7%.
Embodiment 17
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 20 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 94.2%, and 2-chloro-3-chloromethyl thiophene productive rate is 77.4%.
Embodiment 18
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 60 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 99.3%, and 2-chloro-3-chloromethyl thiophene productive rate is 77.3%.
Embodiment 19
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 30 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 99.1%, and 2-chloro-3-chloromethyl thiophene productive rate is 90.5%.
Embodiment 20
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 8 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 99.9%, and 2-chloro-3-chloromethyl thiophene productive rate is 92.1%.
Embodiment 21
Take by weighing 2-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0006mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 97.3%, and 2-chloro-3-chloromethyl thiophene productive rate is 88.9%.
Embodiment 22
Take by weighing 3 methyl thiophene 0.98g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-butyl-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3 methyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 2 hours; Resultant thick product is carried out underpressure distillation, and the 3 methyl thiophene transformation efficiency is 92.4%, and 3-methyl-2-chloromethyl thiophene productive rate is 79.1%.
Embodiment 23
Take by weighing 2-chloro-3 bromo thiophene 1.975g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-chloro-3 bromo thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 50 ℃, reacted 8 hours; Resultant thick product is carried out underpressure distillation, and 2-chloro-3 bromo thiophene transformation efficiency is 92.5%, and 2-chloro-3-bromo-5-chloromethyl thiophene productive rate is 76.9%.
Embodiment 24
Take by weighing 2-bromothiophene 1.63g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-bromothiophene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 30 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and 2-bromothiophene transformation efficiency is 92.7%, and 2-bromo-5-chloromethyl thiophene productive rate is 84.4%.
Embodiment 25
Take by weighing 3 bromo thiophene 1.63g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-heptyl-3-Methylimidazole 0.0006mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3 bromo thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 60 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and the 3 bromo thiophene transformation efficiency is 92.9%, and 3-bromo-2-chloromethyl thiophene productive rate is 76.6%.
Embodiment 26
Take by weighing 3-chlorothiophene 1.185g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0005mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-chlorothiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 50 ℃, reacted 8 hours; Resultant thick product is carried out underpressure distillation, and 3-chlorothiophene transformation efficiency is 98.7%, and 3-chloro-2-chloromethyl thiophene productive rate is 87.0%.
Embodiment 27
Take by weighing 2 respectively, 5-dibromo thiophene 2.42g (0.01mol), Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-propyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; With ionic liquid, 2,5-dibromo thiophene, Paraformaldehyde 96, concentrated hydrochloric acid add in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 10 hours; Resultant thick product is carried out underpressure distillation, 2,5-dibromo thiophene transformation efficiency is 96.2%, 2,5-two bromo-3-chloromethyl thiophene productive rates are 80.4%.
Embodiment 28
Take by weighing 2-thiotolene 0.98g (0.01mol) respectively, formaldehyde 0.75g (0.025mol), ionic liquid bromo 1-amyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-thiotolene, formaldehyde, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 30 ℃, reacted 8 hours; Resultant thick product is carried out underpressure distillation, and 2-thiotolene transformation efficiency is 93.2%, and 2-methyl-5-chloro thiotolene productive rate is 82.1%.
Embodiment 29
Take by weighing 2-iodothiophen 2.10g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-butyl-3-Methylimidazole 0.0004mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-iodothiophen, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-iodothiophen transformation efficiency is 92.6%, and 2-iodo-3-chloromethyl thiophene productive rate is 81.0%.
Embodiment 30
Take by weighing 2-propyl group thiophene 1.26g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-amyl group-3-Methylimidazole 0.0008mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-propyl group thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 60 ℃, reacted 3 hours; Resultant thick product is carried out underpressure distillation, and 2-propyl group thiophene transformation efficiency is 90.3%, and 2-propyl group-5-chloromethyl thiophene productive rate is 76.1%.
The embodiment hentriaconta-
Take by weighing 3-butyl thiophene 1.40g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-butyl-3-Methylimidazole 0.0009mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-butyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 50 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and 3-butyl thiophene transformation efficiency is 86.9%, and 3-butyl-2-chloromethyl thiophene productive rate is 75.9%.
Embodiment 32
Take by weighing 2-amylic thiophene 1.54g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-ethyl-3-Methylimidazole 0.0003mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 2-amylic thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-amylic thiophene transformation efficiency is 89.9%, and 2-amyl group-5-chloromethyl thiophene productive rate is 78.3%.
Embodiment 33
Take by weighing 3-heptyl thiophene 1.82g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-dodecyl-3-Methylimidazole 0.0006mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-heptyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 50 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and 3-heptyl thiophene transformation efficiency is 92.1%, and 3-heptyl-2-chloromethyl thiophene productive rate is 80.3%.
Embodiment 34
Take by weighing 3-octyl group thiophene 1.96g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-octyl group-3-Methylimidazole 0.0009mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-octyl group thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 60 ℃, reacted 4 hours; Resultant thick product is carried out underpressure distillation, and 3-octyl group thiophene transformation efficiency is 96.1%, and 3-octyl group-2-chloromethyl thiophene productive rate is 83.8%.
Embodiment 35
Take by weighing 3-nonyl thiophene 2.10g (0.01mol) respectively, Paraformaldehyde 96 0.75g (0.025mol), ionic liquid bromo 1-heptyl-3-Methylimidazole 0.0012mol, concentrated hydrochloric acid (36%) 4ml; Ionic liquid, 3-nonyl thiophene, Paraformaldehyde 96, concentrated hydrochloric acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 45 ℃, reacted 5 hours; Resultant thick product is carried out underpressure distillation, and 3-nonyl thiophene transformation efficiency is 94.2%, and 3-nonyl-2-chloromethyl thiophene productive rate is 81.8%.
Embodiment 36
Among the embodiment 21, separate the ionic liquid that obtains, do not carry out any processing, directly add 2-chlorothiophene 1.185g (0.01mol), Paraformaldehyde 96 0.75g (0.025mol), concentrated hydrochloric acid (36%) 4ml, magnetic agitation, and under 40 ℃, reacted 6 hours; Resultant thick product is carried out underpressure distillation, and 2-chlorothiophene transformation efficiency is 95.6%, and 2-chloro-3-chloromethyl thiophene productive rate is 85.5%.
Claims (8)
2. the method for claim 1, it is characterized in that: above-mentioned thiophene derivant is substituted thiophene, thionaphthene or substituted benzene thiophthene.
3. the method for claim 1 is characterized in that: substituent X in the aforesaid equation and Y are any two combinations in hydrogen, halogen, 12 carbon following alkyl, cyano group or the ethanoyl.
4. method as claimed in claim 3 is characterized in that: described halogen is chlorine, bromine or iodine.
5. method as claimed in claim 3 is characterized in that: the following alkyl of described 12 carbon is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.
6. the method for claim 1, it is characterized in that: used ionic liquid is bromo 1-ethyl-3-Methylimidazole, bromo 1-sec.-propyl-3-Methylimidazole, bromo 1-butyl-3-Methylimidazole, bromo 1-amyl group-3-Methylimidazole, bromo 1-hexyl-3-Methylimidazole, bromo 1-heptyl-3-Methylimidazole, bromo 1-octyl group-3-Methylimidazole, bromo 1-dodecyl-3-Methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole perfluoro octyl sulfonic acid salt, 1-butyl-3-Methylimidazole hexafluorophosphate or chloro 1-butyl-3-Methylimidazole.
7. the method for claim 1 is characterized in that: the amount that adds catalyst ion liquid is add 1%~16% of thiophene derivant molar weight, and temperature of reaction is at 0~70 ℃, normal pressure, 1~12 hour reaction times.
8. the method for claim 1 is characterized in that: the amount that adds catalyst ion liquid for add 2%~12% of thiophene derivant molar weight, temperature of reaction is at 20~50 ℃, the reaction times is 4~10 hours.
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